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Williams was born in Bristol, UK.[3][4] She has always been known as "Maisie" after the character from the comic strip The Perishers.[5] Williams is the youngest of four children; her three older siblings are James, Beth and Ted.[5] Born to Hilary Pitt (now Frances),[6] a former university course administrator, she grew up in Clutton, Somerset.[4][7] She attended Clutton Primary School and Norton Hill School in Midsomer Norton, before moving to Bath Dance College to study Performing Arts.[8][9]

Williams also signed on to play Lorna Thompson in the sci-fi film We Are Monsters, which was set for a 2014 release.[25]

In 2014, Williams portrayed Lydia in the British film The Falling, which premiered on 11 October 2014, and was released on 24 April 2015 in the UK.[7][26] In December, Williams was in talks with Naughty Dog to star as Ellie in the film adaptation of the video game The Last of Us.[27][28]